三氟甲基取代的4-苯乙烯基香豆素衍生物的合成  

Synthesis of trifluoromethyl substituted 4-styryl coumarin derivatives

作　　者：刘伟 陈芬芬 韩小瑜[1] 王永江[1] LIU Wei;CHEN Fenfen;HAN Xiaoyu;WANG Yongjiang(School of Biological and Chemical Engineering,Zhejiang University of Science and Technology,Hangzhou 310023,Zhejiang,China)

机构地区：[1]浙江科技学院生物与化学工程学院,杭州310023

出　　处：《浙江科技学院学报》2023年第1期1-6,47,共7页Journal of Zhejiang University of Science and Technology

基　　金：浙江省基础公益研究计划项目(LGJ22B020001)。

摘　　要：【目的】设计合成结构新颖的香豆素衍生物,有利于探索发现更多含香豆素骨架化合物的生物活性及应用价值,因而报道了一种三氟甲基取代的苯乙烯基香豆素衍生物的合成方法。【方法】采取不同取代基的3-氰基-4-甲基-香豆素和2,2,2-三氟-1-苯基乙烷-1-酮为反应起始原料,乙酸乙酯为反应溶剂,在室温条件下以DBU(1,8-二氮杂双环[5.4.0]十一碳-7-烯)为催化剂,经vinylogous-aldol(插烯羟醛)重排反应生成三氟甲基取代的苯乙烯基香豆素类化合物。【结果】产物经核磁1H NMR、13C NMR、19F NMR、高分辨质谱及X射线单晶衍射表征;制备了以E(反)式构型为主的8个三氟甲基取代的4-苯乙烯基香豆素化合物,产率最高可达95%。【结论】本研究结果为含氟苯乙烯基香豆素类化合物的合成提供了一种制备方法。[Objective] The design and synthesis of coumarin derivatives with novel structure is beneficial to explore and discover more compounds containing coumarin backbone with biological activities and application values, so the synthesis method of a trifluoromethyl substituted styryl coumarin derivative was proposed. [Method] A series of trifluoromethyl substituted styryl coumarins were synthesized from substituted 3-cyano-4-methyl-coumarins and 2-trifluoro-1-phenylethane-1-one through a vinylogous-aldol rearrangement reaction under the DBU(1,8-Diaza-bicyclo[5.4.0]undec-7-ene) catalysis at the room temperature by using ethyl acetate as the reaction solvent. [Result] Products are characterized by ~1H NMR,13C NMR,19F NMR, high resolution mass spectrometry ESI-MS and X-ray single crystal diffraction. Finally, eight trifluoromethyl substituted 4-styryl coumarins with high E(trans) selectivity are synthesized with up to 95% yield. [Conclusion] This provides a preparation method for the synthesis of fluorobenzene vinyl coumarins.

关 键 词：三氟甲基 苯乙烯基 香豆素衍生物 插烯羟醛重排 

分 类 号：O621.36[理学—有机化学]